trans-bis(ferrocenylethynyl)-bis(triethylphosphine)platinum(II) (2)
CuI (10 mg, 0.05 mmol) was added to a solution of trans -dichlorobis(triethylphosphine) platinum(II) (250 mg, 0.5 mmol, 1 eq) and ethynylferrocene (210 mg, 1 mmol, 2 eq) in degassed diethylamine (10 mL). The solution was stirred at room temperature during 2 hours. Solvents were removed under reduced pressure and the crude material was column chromatographed (SiO
2
: cyclohexane/Et
2
O, (0-5%)). The product was isolated as an orange solid (300 mg, 70%).
MS: (DCI/NH
3
) 850 [M+H]
+
; High Resolution LSI Calculated [M]
+
: 849.1578
(C
36
H
48
Fe
2
P
2
Pt) Found: 849.1601 (100% [M]
+
);
Mp = 193°C.
1
H NMR: (250 MHz, CDCl
3
)

4.20 (4H, t, J = 1.6 Hz, subst. Cp), 4.13 (10H, s, Cp),
4.04 (4H, t, J = 1.6 Hz, subst. Cp), 2.17 (12H, m, C H
2
CH
3
), 1.24 (18H, m, CH
2
C H
3
);
13
C
NMR: (100 MHz, CD
2
Cl
2
)

104.44; 102.72; 73.13; 70.07; 69.27; 66.93; 16.32; 8.21;
31
P
NMR (160 MHz, CDCl
3
)

: 10.98 (s, J
195 Pt-P
= 2391 Hz).

trans-chloro-(ferrocenylethynyl)-bis(triethylphosphine)platinum(II) (3)
Trans -dichlorobis(triethylphosphine)platinum(II) (250 mg, 0.5 mmol, 1 eq) and ethynylferrocene (105 mg, 0.5 mmol, 1 eq) were dissolved in a mixture of chloroform (4 mL) and diethylamine (1 mL). The mixture was heated in a sealed tube at 113°C under microwave irradiation over a 15-min period. Solvents were removed under reduced pressure and the crude material was column chromatographed (SiO
2
: cyclohexane/Et
2
O
(0-5%)). The product was isolated as an orange solid (290 mg, 86%).
MS: (DCI/NH
3
) 677 [M+H]
+
; High Resolution LSI Calculated [M]
+
: 675.1213
(C
24
H
39
ClFeP
2
Pt) Found: 675.1251 (100% [M]
+
);
Mp = 94°C.
1
H NMR: (250 MHz, CDCl
3
)

4.20 (2H, t, J = 1.8 Hz, subst. Cp), 4.12 (5H, s, Cp), 4.05
(2H, t, J = 1.8 Hz, subst. Cp), 2.06 (12H, m, C H
2
CH
3
), 1.20 (18H, m, CH
2
C H
3
);
13
C
NMR: (100 MHz, CD
2
Cl
2
)

96.70; 76.47; 72.72; 70.82; 69.35; 67.07; 14.49; 7.86;
31
P
NMR: (160 MHz, CDCl
3
)

14.77 (s, J
195 Pt-P
= 2405 Hz).

trans-(triisopropysilyl)ethynyl-(ferrocenylethynyl)bis(triethylphosphine)platinum(II) (4)
CuI (20 mg, 0,1 mmol, 0.3 eq) and TIPSA (0.1 mL, 0.44 mmol, 1.3 eq) were added to a solution of trans -chloro-(ferrocenylethynyl)-bis(triethylphosphine)platinum(II) ( 3 ) (230 mg, 0.34 mmol, 1 eq) in degassed diethylamine (5 mL). The solution was stirred at room temperature during 40 min. Solvents were removed under reduced pressure and the crude material was column chromatographed (SiO
2
: cyclohexane/Et
2
O (0-5%)). The product was isolated as an orange solid (200 mg, 72%). MS: (DCI/NH
3
) 822 [M+H]
+
.
1
H NMR:
(250 MHz, CDCl
3
)

4.22 (2H, broad s, subst. Cp), 4.13 (5H, s, Cp), 4.05 (2H, broad s, subst. Cp), 2.15 (12H, m, C H
2
CH
3
), 1.19 (18H, m, CH
2
C H
3
), 1.04 (21H, m, TIPS);
31
P
NMR: (160 MHz, CDCl
3
)

11.30 (s, J
195 Pt-P
= 2409 Hz).
trans-ethynyl(ferrocenylethynyl)-bis(triethylphosphine)platinum(II) (5)
CuI (10 mg, 0.05 mmol) was added to a solution of trans -chloro-(ferrocenylethynyl)bis(triethylphosphine)platinum(II) ( 3 ) (290 mg, 0.43 mmol) in degassed diethylamine (5 mL). Acetylene was bubbled in the solution with stirring at room temperature for 20 min.
Solvents were removed under reduced pressure and the crude material was column chromatographed (SiO
2
: cyclohexane/Et
2
O (0-5%)). The product was isolated as an orange solid (250 mg, 87%). MS: (FAB
+
, MNBA) 665 [M]
+
; High Resolution LSI
Calculated [M] + : 665.1602 (C
26
H
40
FeP
2
Pt) Found: 665.1633 (100% [M] + ); Mp = 71°C.
1
H NMR: (250 MHz, CDCl
3
)

4.19 (2H, t, J = 2.0 Hz, subst. Cp), 4.10 (5H, s, Cp), 4.02
(2H, t, J = 2.0 Hz, subst. Cp), 2.16 (1H, s, H alkyne, 2.13 (12H, m, C H
2
CH
3
), 1.18 (18H, m, CH
2
C H
3
);
13
C NMR: (100 MHz, CD
2
Cl
2
)

104.24; 102.28; 100.61; 94.03; 72.94;
70.08; 69.31; 66.96; 16.05; 8.11;
31
P NMR: (160 MHz, CDCl
3
)

10.70 (s, J
195 Pt-P
= 2380
Hz).
1,2,3,4,5-penta(4-(triisopropylsilylacetylene)phenyl)cyclopentadiene (8)
In a Schlenk tube, 1-bromo-1,2,3,4,5-penta(4-bromophenyl)cyclopentadiene ( 6 ) (300 mg,
0.32 mmol, 1 eq), TIPSA (1.4 mL, 6.4 mmol, 20 eq), diisopropylamine (2 mL) and

freshly distilled THF (4 mL) were degassed under argon during 20 min. CuI (12 mg, 0.06 mmol, 20 mol %) and Pd(PPh
3
)
4
(40 mg, 0.03 mmol, 10 mol %) were added and the mixture was heated at 80°C overnight. The same amounts of additional CuI, TIPSA and
Pd
0
were added and the mixture was heated at 80°C for another 24 hours. Solvents were removed under reduced pressure and the crude material was column chromatographed
(SiO
2
, cyclohexane/CH
2
Cl
2
(0-10%)) to give a fluorescent yellow glassy solid (350 mg,
81 %). MS: (DCI/NH
3
) 1349 [MH] + , 1381 [M+2NH
3
] + ; High Resolution LSI Calculated
[M] + : 1346.8706 (C
90
H
126
Si
5
) Found: 1346.8787 (100% [M] + ). 1 H NMR: (250 MHz,
CD
2
Cl
2
)

7.34 (d, 6H, J = 8 Hz, H b-f
), 7.21 (d, 4H, J = 8 Hz, H d
), 7.17 (d, 2H, J = 8 Hz,
H a
), 7.02 (d, 4H, J = 8 Hz, H e
), 6.96 (d, 4H, J = 8 Hz, H c
), 5.16 (s, 1H, H g
), 1.14 (m, 105
H, TIPS);
13
C NMR: (100 MHz, CD
2
Cl
2
)

146.80; 144.11; 137.92; 135.71; 135.23;
132.37; 131.74; 131.49; 129.95; 128.76; 128.30; 122.24; 122.02; 121.74; 106.83; 106.78;
106.72; 91.34; 91.23; 90.57; 62.11; 18.43; 18.39; 11.30; 11.26.
1-bromo-1,2,3,4,5-penta(4-(triisopropylsilylacetylene)phenyl)cyclopentadiene (9)
In a Schlenk tube, 1,2,3,4,5-penta(4-(triisopropylsilylacetylene)phenyl)cyclopentadiene
( 8 ) (380 mg, 0.28 mmol, 1 eq) was dissolved in freshly distilled THF (10 mL). n
BuLi
(0.28 mmol, 1 eq) was added dropwise under argon at -78°C and the mixture was stirred at this temperature for 30 min. NBS (55 mg, 0.30 mmol, 1.1 eq) was subsequently added and the mixture was stirred at -78°C for 30 min. The temperature was left to raise slowly to room temperature. Solvents were removed under reduced pressure and the crude material was column chromatographed (SiO
2
, cyclohexane) to give an orange glassy solid
(220 mg, 55 %).MS: (DCI/NH
3
) 1427 [MH]
+
, 1444 [M+NH
4
]
+
; High Resolution LSI
Calculated [M] + : 1424.7811 (C
90
H
125
BrSi
5
) Found: 1424.7897 (100% [M] + ). 1 H NMR:
(500 MHz, CDCl
3
)

7.36 (broad s, 4H, H a-b
), 7.28 (d, 4H, J = 8 Hz, H f
), 7.21 (d, 4H, J =
8 Hz, H d
), 6.89 (d, 4H, J = 8 Hz, H e
), 6.88 (d, 4H, J = 8 Hz, H c
), 1.15 (s, 21H, TIPS),
1.14 (s, 42H, TIPS), 1.11 (s, 42H, TIPS);
13
C NMR: (125 MHz, CDCl
3
)

148.34;
141.55; 135.27; 134.03; 133.52; 132.32; 131.86; 131.56; 131.4; 130.08; 129.80; 127.36;
123.32; 122.69; 122.51; 106.90; 106.81; 106.37; 91.81; 91.64; 91.51; 75.35; 18.67;
11.32.

Bromo-

5 -1,2,3,4,5-penta[4-(triisopropylsilylacetylene)phenyl]cyclopentadienyl dicarbonyl ruthenium(II) (10)
Ruthenium carbonyl (37 mg, 0.058 mmol, 1eq) and 1-bromo-1,2,3,4,5-penta(4-
(triisopropylsilylacetylene)phenyl)cyclopentadiene ( 9 ) (250 mg, 0.17 mmol, 3 eq) were heated under argon at reflux for 2 hours in 4 mL of freshly distilled toluene. The solution, initially yellow, rapidly turned to dark green and then to cherry red. Solvents were removed under reduced pressure and the crude material was column chromatographed
(SiO
2
, cyclohexane/CH
2
Cl
2
(0-10 %)) to give a yellow solid (200 mg, 72%). MS:
(DCI/NH
3
) 1618 [M+2NH
3
] + , 1601 [M+NH
3
] + , 1563 [M+2NH
3
-2CO] + , 1545 [M+NH
3
-
2CO]
+
, 1528 [M-2CO]
+
; High Resolution LSI Calculated [M]
+
: 1582.6753
(C
92
H
125
BrO
2
RuSi
5
); Mp = 180°C (with decomposition). 1
H NMR: (250 MHz, CD
2
Cl
2
)

7.28 (d, 10H, J = 8.6 Hz, H o
), 7.00 (d, 10H, J = 8.6 Hz, H m
), 1.13 (s, 105H, TIPS);
13
C
NMR: (100 MHz, CD
2
Cl
2
)

196.17; 132.28; 131.70; 129.36; 123.99; 106.31; 105.99;
92.76; 18.53; 11.43; IR:

C=O
2004 (s) and 2048 (s) cm
-1
.

5 -1,2,3,4,5-penta[4-(triisopropylsilylacetylene)phenyl]cyclopentadienyl hydrotris
(indazol-1-yl)borate ruthenium(II) (11)
Bromo-
 5 -1,2,3,4,5-penta(4-(triisopropylsilylacetylene)phenyl)cyclopentadienyl dicarbonyl ruthenium(II) ( 10 ) (200 mg, 0.12 mmol, 1 eq) and potassium hydrotris(indazol-1-yl)borate (102 mg, 0.25 mmol, 2 eq) were heated under reflux for 24 hours in 5 mL of freshly distilled THF. Solvents were removed under reduced pressure and the crude material was column chromatographed (SiO
2
, cyclohexane) to give a mixture of two yellow products (80 mg) which were used without further purification in the next step. An analytically pure sample was obtained after a second column chromatography (SiO
2
, cyclohexane). MS: (APCI) 1812 [M] + ; High Resolution LSI
Calculated [M]
+
: 1810.9201 (C
111
H
141
BN
6
RuSi
5
) Found: 1811.2489 [M]
+
.
1
H NMR: (500
MHz, CD
2
Cl
2
)

8.04 (d, 3H, J = 7.9 Hz, H e
), 7.93 (s, 3H, H a
), 7.45 (d, 3H, J = 8.3 Hz,
H b
), 7.4 (m, 3H, H c
), 7.37 (d, 10H, J = 8.6 Hz, H o
), 7.19 (d, 10H, J = 8.6 Hz, H m
), 7.05
(m, 3H, H d
), 1.11 (m, 105H, TIPS);
13
C NMR: (125 MHz, CD
2
Cl
2
)

143.46; 140.45;
133.76; 133.41 , 130.89; 126.46; 122.98; 122.46; 120.42; 119.98; 111.43; 106.63; 91.52;
87.62; 18.37; 11.24.


5 -1,2,3,4,5-penta[4-(ethynyl)phenyl]cyclopentadienyl hydrotris(indazol-1-yl)borate ruthenium(II) (12)
 5
-1,2,3,4,5-penta(4-(triisopropylsilylacetylene)phenyl)cyclopentadienyl hydrotris(indazol-1-yl)borate ruthenium(II) ( 11 ) (20 mg, 0.011 mmol, 1 eq) was dissolved in 2 ml of 1M TBAF in THF (2 mmol, 180 eq) with 5 vol. % of water. The solution was stirred at room temperature overnight. Solvents were removed under reduced pressure and the crude material was column chromatographed (SiO
2
, cyclohexane/CH
2
Cl
2
(0-10 %)) to give a yellow solid (6 mg, 52 %). MS: (APCI) 1030
[M]
+
;
1
H NMR: (250 MHz, CD
2
Cl
2
)

7.94 (d, 3H, J = 9.3 Hz, H e
), 7.82 (s, 3H, H a
), 7.31
(d, 3H, J = 7.7 Hz, H b
), 7.29 (m, 3H, H c
), 7.27 (d, 10H, J = 8.6 Hz, H o
), 7.10 (d, 10H, J =
8.6 Hz, H m
), 6.95 (m, 3H, H d
), 3.05 (s, 5H, C H ).

5 -1,2,3,4,5-penta[4-{trans-ethynyl-(ethynylferrocenyl)bis(triethylphosphine)platinum(II)} phenyl] cyclopentadienyl hydrotris(indazol-1yl)borate ruthenium(II) (13)
In a Schlenk tube,
 5 -1,2,3,4,5-penta(4-(ethynyl)phenyl)cyclopentadienyl hydrotris(indazol-1-yl)borate ruthenium(II) freshly prepared ( 12 ) (12 mg, 0.011 mmol, 1 eq), THF (2 mL) and diethylamine (1 mL) were degassed under argon during 20 min.
Trans -chloro-(ferrocenylethynyl)-bis(triethylphosphine)platinum(II) ( 3 ) (50 mg, 0.073 mmol, 6.3 eq) and CuI (2 mg, 0.010 mmol, 0.9 eq) were added and the mixture was stirred at room temperature for 8 hours. The same amounts of additional CuI and platinum complex were added and the solution was stirred at room temperature overnight. Solvents were removed under reduced pressure and the crude material was column chromatographed (SiO
2
, cyclohexane/Et
2
O (0-20 %)) to give an orange solid (20 mg, 41%). MS: (ES/MS) 2112 [M]
2+
, 1409 [M]
3+
; (MALDI-TOF) 4226.2 [M]
+
(calc
4226.98);
1
H NMR: (500 MHz, CD
2
Cl
2
)

8.04 (d, 3H, J = 6.8 Hz, H e
), 8.02 (s, 3H, H a
),
7.45 (d, 3H, J = 8.7 Hz, H b
), 7.38 (m, 3H, H c
), 7.25 (d, 10H, J = 8.5 Hz, H o
), 7.03 (t, 3H,
J = 7.6 Hz, H d
), 6.97 (d, 10H, J = 8.5 Hz, H m
), 4.22 (t, 10H, J = 1.8 Hz, subst. Cp), 4.15
(s, 25H, Cp), 4.07 (t, 10H, J = 1.8 Hz, subst. Cp), 2.17 (m, 60H, CH
2
) 1.22 (m, 90H,
CH
3
);
13
C NMR: (125 MHz, CD
2
Cl
2
)

143.37; 140.31; 133.24; 130.92; 129.61; 127.69;

126.01; 123.06; 120.03; 119.98; 111.36; 109.21; 108.78; 104.86; 102.62; 87.52; 72.95;
70.09; 69.31; 66.97; 16.23; 8.15; 31 P NMR: (200 MHz, CD
2
Cl
2
)

11.30 (s, J
195 Pt-P
= 2374
Hz); 195 Pt NMR: (500 MHz, CD
2
Cl
2
)

- 4742; UV/Vis (CH
2
Cl
2
;  max
(  )=264 (225000),
306 (169200), 359 (58000), 436 (10400). CV(CH
2
Cl
2
, n Bu
4
NPF
6
,), E
Fe(II)-Fe(III)
(V/SCE):
+0.31 rev, (5 e) ; E
Ru(II):Ru(III)
(V/SCE): 0.60 rev (1 e) (Sweep rate: 100 mV.s
-1 ).
 5 -1,2,3,4,5-penta[4-{ trans -ethynyl-(ethynylferrocenyl)bis(triethylphosphine)platinum(II)} phenyl] cyclopentadienyl hydrotris[6-
(ethoxycarbonyl) indazol-1-yl]borate ruthenium(II) (8)
In a Schlenk tube,  5 -1,2,3,4,5-penta(4-(ethynyl)phenyl)cyclo pentadienylhydrotris[6-
(ethoxycarbonyl) indazol-1-yl]borate ruthenium(II) ( 14 ) (16 mg, 0.013 mmol, 1 eq), THF
(2 mL) and diethylamine (1 mL) were degassed under argon during 20 min. Trans chloro-(ferrocenylethynyl)-bis(triethyl phosphine)platinum(II) ( 5 ) (50 mg, 0.073 mmol,
5.6 eq) and CuI (5 mg, 0.010 mmol, 2 eq) were added and the mixture was stirred at room temperature for 8 hours. The same amounts of additional CuI and platinum complex were added and the solution was stirred at room temperature overnight. Solvents were removed under reduced pressure and the crude material was column chromatographed (SiO
2
, cyclohexane/Et
2
O (0-20 %)) to give an orange solid (20 mg, 35%). MS: (MALDI-TOF)
4442.4 [M] + (calc 4442.19); 1 H NMR: (500 MHz, C
6
D
6
)  9.24 (s, 3H, H d
), 8.70 (s, 3H,
H a
), 8.02 (d, 3H, J = 7.2 Hz, H c
), 7.78 (d, 10H, J = 7.6 Hz, H o
), 7.36 (d, 10H, J = 7.6 Hz,
H m
), 6.99 (d, 3H, J = 7.2 Hz, H b
), 4.53 (s broad, 10H, subst. Cp), 4.33 (s, 25H, Cp), 4.1
(q, 6H, J = 6.4 Hz, OC H
2
CH
3
), 4.12 (s broad, 10 H, subst. Cp), 2.09 (m, 60H, CH
2
), 1.43
(t, 9H, J = 6.4 Hz, OCH
2
C H
3
), 1.22 (m, 90H, CH
3
); 13 C NMR: (125 MHz, C
6
D
6
) 
166.40; 143.55; 140.99; 133.73; 130.32; 125.90; 121.30; 120.30; 113.94; 70.51; 69.61;
67.29; 60.61; 16.57; 8.33;
195 Pt NMR: (500 MHz, C
6
31
D
6
P NMR: (200 MHz, C
)  - 4745.
6
D
6
)  11.30 (s, J195
Pt-P
= 2393 Hz); cm -1 .
 5 -1,2,3,4,5-penta-(4-(triisopropylsilylacetylene)phenyl) cyclopentadienyl hydrotris [6-(ethoxycarbonyl) indazol-1-yl] borate ruthenium(II) (13)
Bromo 5 -1,2,3,4,5-penta(4-(triisopropylsilylacetylene) phenyl)cyclopentadienyle dicarbonyl ruthenium (II) ( 12 ) (160 mg, 0.1 mmol, 1eq) and potassium hydrotris[6-
(ethoxycarbonyl)indazol-1-yl]borate (125 mg, 0.2 mmol, 2eq) were heated in a sealed tube at 150 °C under microwave irradiation during 10 minutes in a mixture of 2 ml of acetonitrile and 1 ml of DMF. The crude reaction mixture was evaporated under vacuum.
The product was adsorbed on silica and purified by column chromatography (SiO
2
,
Cyclohexane/CH
2
Cl
2
80 %) to a yellow solid (35 mg, 17%). MS: (APCI) 2029 [M+H] + ;
High Resolution LSI Calculated [M]+: 2026.9835 (C
120
H
153
BBrO
2
N
6
O
6
RuSi
5
) Found:
2026.9872 (100% [M]+); 1 H NMR: (250 MHz, CD
2
Cl
2
)  8.76 (s, 3H, H a
), 7.99 (s, 3H,

H d
), 7.68 (d, 3H, J = 8.6 Hz, H c
), 7.46 (d, 3H, J = 8.6 Hz, H b
), 7.31 (d, 10H, J = 8.2 Hz,
H o
), 7.17 (d, 10H, J = 8.2 Hz, H m
), 4.47 (q, 6H, J = 7.1 Hz, CH
2
), 1.48 (t, 9H, J = 7.1
Hz,CH
3
), 1.08 (m, 105H, TIPS); 13 C NMR: (63 MHz, CD
2
Cl
2
)  166.80; 143.11; 140.84;
133.31; 133.04; 131.04; 129.03; 125.31; 122.78; 121.03; 119.81; 113.86; 106.53; 91.85;
88.53; 61.25; 18.39; 14.25; 11.28.
 5 -1,2,3,4,5-penta[4-(ethynyl)phenyl]cyclopentadienyl
(ethoxycarbonyl) indazol-1-yl] borate ruthenium(II) (14) hydrotris [6-
 5 -1,2,3,4,5-penta-(4-(triisopropylsilylacetylene)phenyl) cyclopentadienyl hydrotris [6-
(ethoxycarbonyl) indazol-1-yl] borate ruthenium(II) ( 13 ) (30 mg, 0.015 mmol, 1eq) was dissolved in 2 ml of TBAF 1M in THF (2 mmol, 135 eq) with 5% of water. The solution was stirred at room temperature overnight and the solvent was evaporated. The crude product was purified by column chromatography (SiO
2
, CH
2
Cl
2
) to give a yellow solid
(10 mg, 54 %). MS: (APCI) 1246 [M] + ; 1 H NMR: (250 MHz, CD
2
Cl
2
)  8.76 (s, 3H, H a
),
7.98 (s, 3H, H d
), 7.68 (d, 3H, J = 8.5 Hz, H c
), 7.44 (d, 3H, J = 8.5 Hz, H b
), 7.31 (d, 10H,
J = 8.4 Hz, H o
), 7.17 (d, 10H, J = 8.4 Hz, H m
), 4.47 (q, 6H, J = 7.1 Hz, CH
2
), 3.11 (s,
5H, CH), 1.48 (t, 9H, J = 7.1 Hz,CH
3
); 13 C NMR: (63 MHz, CD
2
Cl
2
)  166.85; 143.19;
140.83; 133.82; 133.43; 131.32; 129.21; 125.38; 121.53; 121.18; 119.85; 113.95; 88.48;
83.04; 78.16; 61.36; 14.32.